CN103228722B

CN103228722B - Polymeric composition and sealant layer with same

Info

Publication number: CN103228722B
Application number: CN201180057081.3A
Authority: CN
Inventors: 梁文斌; K.L.沃尔顿; G.R.马钱德
Original assignee: Dow Global Technologies LLC
Current assignee: Dow Global Technologies LLC
Priority date: 2010-09-30
Filing date: 2011-09-29
Publication date: 2015-06-24
Anticipated expiration: 2031-09-29
Also published as: BR112013007274A2; UA110497C2; US8921484B2; JP2013542285A; ES2631553T3; MX2013003614A; EP2622013A1; WO2012044732A1; RU2013119989A; PL2622013T3; BR112013007274B1; CN103228722A; EP2622013B1; JP5968321B2; US20130177720A1

Abstract

Disclosed herein is a polymeric composition. The polymeric composition includes: (A) a propylene-based polymer; (B) an ethylene/alpha-olefin polymer; and (C) a block composite comprising: i) a propylene-based crystalline polymer; ii) an ethylene/alpha-olefin polymer; and iii) a block copolymer comprising a propylene-based crystalline block and an ethylene/alpha-olefin block. The polymeric composition provides improved heat seals when formed into a film, a film layer, or flexible containers such as a retort pouch.

Description

Polymer composition and the sealant layer with this polymer composition

Background technology

Plastic film can be used for multiple packaging application, such as bag, container, cup, matrass (retort), pipe, and plate.There is the layered product of hot sealable layer, unitary film and multilayer film and be generally used for " shaping, fill and sealing " (FFS) machine.FFS machine produces the Continuous Flow of packaging by film, and this packaging can be closed by intermembranous sealer.

Intermembranous heat seal is closed following to be formed: applying pressure and placing film between the relative heat seal narrow orifice also applying the heat of the sealing kick off temperature higher than film.The heat seal made is closed usually the strongest after sealer is cooled to envrionment temperature.For improving turnout, before heat seal thing cools completely, packaging product is filled.Therefore, heat seal is closed and is necessary very rapidly to provide enough intensity, and without the need to packaging is cooled to envrionment temperature.Otherwise, heat seal will be damaged and close, cause product defective, waste product, and increase cost.

And, need the film for distilling packaging to be formed can to stand the heat seal thing of raised temperature needed for sterilizing.Distillation packaging is exposed to the time point of the temperatures extend being greater than 121 ° of C or being greater than 130 ° of C usually, so that by content sterilizing wherein.

Therefore this area thinks lasting needs exploitation for the film of the improvement of FFS application.Especially, need following film, it has low heat seal kick off temperature and strong Hot tack strength so that increase the production efficiency of wrapping process such as FFS process in wide temperature range.The following film of further needs, it also has elevated-temperature seal intensity except above-mentioned film character.

Summary of the invention

The film that the application provides polymer composition and prepared by this polymer composition.When being formed as film (or rete), Inventive polymers compositions table reveals (i) low heat seal kick off temperature, the Hot tack strength that (ii) is strong in wide temperature window, and (iii) high Hot tack strength.And the film comprising Inventive polymers composition has the elevated-temperature seal intensity being suitable for the film be used as in distillation packaging.

The application provides polymer composition.In one embodiment, provide polymer composition, it comprises:

(A) based on the polymkeric substance of propylene;

(B) ethylene/alpha-olefin polymer;

(C) block matrix material, it comprises:

I) based on the crystalline polymer of propylene;

Ii) ethylene/alpha-olefin polymer; With

Iii) segmented copolymer of crystalline blocks based on propylene and ethylene/alpha-olefin block is comprised.

In one embodiment, polymer composition comprises the ethylene/alpha-olefin copolymer of at least 50wt%, based on the gross weight of (A) and (B).

The application provides film.In one embodiment, provide film, it comprises at least one layer formed by polymer composition, and this polymer composition comprises:

(A) based on the polymkeric substance of propylene;

(B) ethylene/alpha-olefin polymer;

(C) block matrix material, it comprises:

I) based on the crystalline polymer of propylene;

Ii) ethylene/alpha-olefin polymer; With

In one embodiment, film comprises the second layer.The second layer comprises the polymkeric substance based on alkene.

The application provides goods.In one embodiment, provide retort pouch, it comprises the first layer, the second layer and optional third layer.The first layer comprises polymer composition, and this polymer composition comprises:

(A) based on the polymkeric substance of propylene;

(B) ethylene/alpha-olefin polymer;

(C) block matrix material, it comprises:

I) based on the crystalline polymer of propylene;

Ii) ethylene/alpha-olefin polymer; With

In one embodiment, the second layer can comprise the polymkeric substance based on alkene.

The advantage of the application is the polymer composition improved, and provides the heat seal character of improvement, such as low heat seal kick off temperature when it is formed as film or rete, and/or the strong Hot tack strength in wide temperature window, and/or high Hot tack strength.

The advantage of the application is the film of the improvement for heat seal application.

Accompanying drawing explanation

Fig. 1 is the orthographic plan of the retort pouch according to the application's embodiment.

Fig. 2 is the front view of the multilayer film according to the application's embodiment.

Fig. 3 is the front view of the multilayer film according to the application's embodiment.

Fig. 4 is the Hot tack strength of display comparison sample and the application's embodiment and the figure of temperature.

Fig. 5 is the figure of the thermal bonding temperature window of display comparison sample and the application's embodiment.

Fig. 6 compares the thermal bonding temperature window of comparative sample and the application's embodiment and the figure of component (A) and component (B) ratio.

Fig. 7 is hot sticky the kick off temperature of display comparison sample and the application's embodiment and component (A) and the figure of component (B) ratio.

Fig. 8 is the heat-seal strength of display comparison sample and the application's embodiment and the figure of temperature.

Fig. 9 is the figure of the frictional coefficient of display comparison sample and the application's embodiment.

Figure 10 is the figure of the Hot tack strength at 150 ° of C of display comparison sample and the application's embodiment.

Figure 11 is the figure of the transparency of display comparison sample and the application's embodiment.

Embodiment

(A) based on the polymkeric substance of propylene;

(B) ethylene/alpha-olefin copolymer; With

(C) block matrix material, it comprises:

I () is based on the crystalline polymer of propylene;

(ii) ethylene/alpha-olefin polymer; With

(iii) segmented copolymer of crystalline blocks based on propylene and ethylene/alpha-olefin block is comprised.

Polymer composition optionally can comprise (D) based on the polymkeric substance of alkene and/or (E) additive.In one embodiment, polymer composition comprises the component (B) of at least 50wt%, based on the gross weight of component (A) and (B).

In another embodiment, polymer composition comprises the component (A) of 1wt% to 50wt%, at least component (B) of 50wt% or at least 50wt% to 95wt%, and the component of 1wt% to 30wt% (C).Weight percent is based on the gross weight of composition.Should be appreciated that, the amount of each component (A)-(E) can be regulated, to obtain the polymer composition of 100wt%.

(A) based on the polymkeric substance of propylene

Polymer composition comprises the polymkeric substance based on propylene, i.e. component (A).Polymkeric substance based on propylene can be alfon or propylene/alpha-olefins interpretation.In one embodiment, the polymkeric substance based on propylene is alfon.The density of alfon is 0.88g/cc to 0.92g/cc, and/or melt flow rate (MFR) is 1.0g/10min to 3.0g/10min, and/or fusing point (Tm) is for being greater than 130 ° of C to 170 ° of C.The limiting examples of suitable alfon is H110-02N, purchased from The DowChemical Company, and Midland, Michigan.

In one embodiment, the polymkeric substance based on propylene is propylene/alpha-olefins interpretation.For the object of the application, think that ethene is alpha-olefin.The limiting examples of suitable comonomer comprises ethene, C _4-20alpha-olefin, such as 1-butylene, 1-amylene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-laurylene, 1-tetradecylene, 1-hexadecylene, and 1-octadecylene; C _4-20diolefine, such as 1,3-butadiene, 1,3-pentadiene, norbornadiene, 5-ethylidene-2-norbornylene (ENB) and Dicyclopentadiene (DCPD); C _8-40vinyl aromatic compounds, comprises vinylbenzene, o-vinyl toluene, m-vinyl toluene, and p-methylstyrene, Vinylstyrene, vinyl biphenyl, vinyl naphthalene; With the C of halogen substiuted _8-40vinyl aromatic compounds, such as chloro-styrene and fluorobenzene ethene.Alpha-olefin also can comprise the ring texture as hexanaphthene or pentamethylene, thus obtains the alpha-olefin as 3-cyclohexyl-1-propylene (allyl cyclohexane) and vinyl cyclohexane.

In one embodiment, propylene/alpha-olefins interpretation is atactic propene/ethylene copolymer.Atactic propene/ethylene copolymer comprises the unit (gross weight based on propylene/ethylene copolymer) that 1wt% to 10wt% is derived from ethene.The density of propylene/ethylene copolymer is 0.88g/cc to 0.92g/cc, and/or melt flow rate (MFR) (MFR) 21.0g/10min to 10g/min, and/or melt temperature (Tm) is greater than 130 ° of C to 170 ° of C.The limiting examples of suitable atactic propene/ethylene copolymer is DS6D81, purchased from TheDow Chemical Company, and Midland, Michigan.

In one embodiment, the molecular weight distribution (MWD) based on the polymkeric substance of propylene is greater than 4.0.In further embodiment, the polymkeric substance based on propylene is the propylene/ethylene copolymer that MWD is greater than 4.0.

Polymkeric substance based on propylene can comprise two or more embodiments disclosed in the present application.

(B) ethylene/alpha-olefin copolymer

Inventive polymers composition comprises ethylene/alpha-olefin copolymer, i.e. component (B).Comonomer can be alpha-olefin, such as C _3-20linearly, the alpha-olefin of branching or ring-type.Suitable C _3-20the limiting examples of alpha-olefin comprises propylene, 1-butylene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-laurylene, 1-tetradecylene, 1-hexadecylene, and 1-octadecylene.Alpha-olefin also can comprise the ring texture as hexanaphthene or pentamethylene, thus obtains the alpha-olefin as 3-cyclohexyl-1-propylene (allyl cyclohexane) and vinyl cyclohexane.Although be not the alpha-olefin of this terminology standard meaning, but for object of the present invention, some cyclic olefin, as norbornylene and relevant alkene thereof, particularly 5-ethylidene-2-norbornylene be also alpha-olefin and can be used in alternative above-mentioned alpha-olefin some or all.Similarly, vinylbenzene and relevant alkene (such as, alpha-methyl styrene etc.) thereof are the alpha-olefins for the object of the invention.Illustrative ethene polymers comprises ethylene/propene copolymer, ethylene/butylene copolymers, ethene/1-hexene copolymer, ethene/1-octene copolymer, ethylene/styrene multipolymer etc.Illustrative terpolymer comprises ethylene/propene/1-octene copolymer, ethylene/propene/butylene copolymer, ethylene/butylene/1-octene copolymer, ethylene/propylene/diene monomer multipolymer (EPDM) and ethylene/butylene/styrol copolymer.Described multipolymer can be multipolymer that is random or block.

In one embodiment, ethylene/alpha-olefin copolymer is the ethylene/alpha-olefin interpolymers (EXXACT of even branching, purchased from ExxonMobil Coroporation, Irving, Texas and TAFMER, purchased from Mitsui), or substantially linear ethene/alpha-olefin interpolymers (AFFINITY and ENGAGE, purchased from The Dow Chemical Company, Midland, Michigan).

In one embodiment, the melt index of ethylene/alpha-olefin polymer is 0.5g/10min, or is 1.0g/10min, or is 25g/10min, or is 15g/10min.

In one embodiment, ethylene/alpha-olefin polymer is substantially linear ethene/alpha-olefinic polymer.Substantially linear ethene/alpha-olefin interpolymers (SLEP) is the polymkeric substance of even branching and is described in United States Patent (USP) 5,272,236; 5,278,272; 6,054,544; 6,335,410 and 6,723,810; The application is incorporated to each via reference.Substantially linear ethene/alpha-olefin interpolymers has long chain branching.Long chain branches has the comonomer distribution identical with polymer main chain, and can have the length approximately identical with main polymer chain length." substantially linear " is usually directed to polymkeric substance, and its average " every 1000 entire carbon atom are by 0.01 long chain branches " to " every 1000 entire carbon atom are by 3 long chain branches " replaces.Compared with the carbon chain lengths by a kind of comonomer being incorporated into the short chain branch that main polymer chain is formed, the length of long chain branches is longer.

Some polymkeric substance can be replaced by 0.01 long chain branches to 3 long chain branches by every 1000 entire carbon atom, be more preferably every 1000 entire carbon atom to be replaced by 0.05 long chain branches to 2 long chain branches, be in particular every 1000 entire carbon atom and replaced by 0.3 long chain branches to 1 long chain branches.

Substantially linear ethene/alpha-olefin interpolymers forms the ethene polymers of the even branching of unique class.They are significantly different from the linear ethylene/alpha-olefin interpolymers (as above discussing) of the even branching of the routine knowing kind, and in addition, their heterogeneous with routine " Ziegler-Natta catalyst is polymerized " linear tetrafluoroethylene polymers (such as, use by people such as Anderson at United States Patent (USP) 4,076, ultra-low density polyethylene (ULDPE), linear low density polyethylene (LLDPE) or high density polyethylene(HDPE) (HDPE) prepared by technology disclosed in 698) neither be identical kind; And the highly-branched polyethylene that they and high pressure, free radical cause (such as, Low Density Polyethylene (LDPE), ethylene-acrylic acid (EAA) multipolymer and ethylene vinyl acetate (EVA) multipolymer) neither be identical kind.

Substantially linear ethene/alpha-olefin interpolymers for even branching of the present invention has superior processibility, even if they have relatively narrow molecular weight distribution is also like this.Unexpectedly, the melt flow ratio (I according to ASTM D1238 of the ethylene interpolymer of substantially linear ₁₀/ I ₂) can extensively change, and substantially with molecular weight distribution (M _w/ M _nor MWD) irrelevant.The linear ethylene interpolymer of this unexpected character and conventional uniform branching (such as by Elston at U.S.3,645, describe in 992 those) and non-homogeneous branching routine " Ziegler-Natta is polymerized " linear polyethylene interpretation (such as by people such as Anderson at U.S.4,076, in 698 describe those) completely contrary.Be different from the ethylene interpolymer of substantially linear, linear ethylene interpolymer (be no matter even branching or non-homogeneous branching) has rheological property, makes, when molecular weight distribution increases, and I ₁₀/ I ₂value also increases.

Long chain branching can by using ¹³c nucleus magnetic resonance (NMR) spectral method is determined, and method (Rev.Micromole.Chem.Phys., C29 (2 & 3), 1989 of Randall can be used, pp.285-297) quantification, its disclosure is by reference to being incorporated to the application.Two kinds of other methods are: with the gel permeation chromatography (GPCLALLS) of Small angle Laser Light Scattering detector coupling, and with the gel permeation chromatography (GPC-DV) of differential viscometer detector coupling.The use of these technology detected for long chain branching and principle were fully proved in the literature.See, such as, Zimm, B.H.and Stockmayer, W.H., J.Chem.Phys., 17,1301 (1949) and Rudin, A., Modern Methods of PolymerCharacterization, John Wiley & Sons, New York (1991) pp.103-112.

In one embodiment, the density of SLEP is less than or equal to 0.91g/cc, or is 0.885g/cc to 0.89g/cc, or is 0.905g/cc.The melt index of SLEP is 0.5g/10min to 2g/10min, and/or melt temperature is 95 ° of C to 105 ° of C.The limiting examples of suitable SLEP is AFFINITYPL1880, and it is purchased from Dow Chemical Company, Midland, Michigan.

As used in this application, " gross weight " is the gross weight of component (A) and component (B).Gross weight evaluates the measuring of component (A) relative to component (B), and vice versa.In other words, gross weight does not comprise component (C).In one embodiment, gross weight comprises component (B) (ethylene/alpha-olefin copolymer) that be greater than 50wt% or be greater than 50wt% to 95wt%.

Polymkeric substance based on ethene can comprise two or more embodiments disclosed in the present application.

(C) block matrix material

Inventive polymers composition comprises block matrix material.Block matrix material comprises:

I () is based on the crystalline polymer of propylene;

(ii) based on the polymkeric substance of ethylene/alpha-olefin; With

Term " segmented copolymer " or " chain segment copolymer " represent the polymkeric substance comprising the different region of two or more chemistry preferably combined in linear mode or segment (being called " block "), that is, the polymkeric substance of the chemofacies anticoincidence unit that the ethylene linkage functionality head and the tail (but not with pendency or grafting mode) comprising being polymerized are connected.In one embodiment, each block is different in the following areas: the amount (comprising long chain branching or hyperbranched) of the quantity of the comonomer wherein introduced or type, density, the amount of degree of crystallinity, the crystallite size being attributable to the polymkeric substance of this composition, stereoregular type or degree (isotaxy or syndiotaxy), region-systematicness or region-irregularity, branching, homogeneity or any other chemistry or physical properties.The feature of the segmented copolymer of the application is, due to the effect of shuttling agent and catalyst combination in a preferred embodiment and the unique distribution of the polymkeric substance polymolecularity (PDI or Mw/Mn) obtained, block length distributes and/or block number distributes.

" block matrix material " is new polymers, it segmented copolymer comprising soft multipolymer, hard polymer and there is soft chain segment and hard segment, wherein the hard segment of segmented copolymer is identical with the composition of hard polymer in block matrix material, and the soft chain segment of segmented copolymer is identical with the composition of the soft multipolymer of block matrix material.Segmented copolymer can be linear or branching.More particularly, when preparing in a continuous process, the PDI of block matrix material is desirably 1.7 to 15, or is 1.8 to 3.5, or is 1.8 to 2.2, or is 1.8 to 2.1.When preparing with interval or semi-batch process, the PDI of block matrix material is 1.0 to 2.9, or is 1.3 to 2.5, or is 1.4 to 2.0, or is 1.4 to 1.8.

" firmly " segment represents the block of the cell height crystallization of polymerization, and wherein the amount of monomer is greater than 95wt%, is preferably greater than 98wt%.In other words, the co-monomer content in hard segment is less than 5wt%, is preferably less than 2wt%.In some embodiments, hard segment comprises all or substantially whole propylene units.On the other hand, " soft " segment represents amorphous, essentially no setting or the elastomeric block of the unit of polymerization, and wherein co-monomer content is greater than 10 % by mole.

(i) block matrix material index (Block Composite Index)

The embodiment of the present invention (table 3,4) shows, insoluble fraction comprises can the ethene of evaluation quantity, if polymkeric substance is simply the blend of iPP homopolymer and EP multipolymer, so this can the ethene of evaluation quantity can not exist.Should " extra ethene " for illustrating, mass balance calculation$ can be carried out to evaluate block matrix material index by the amount of dimethylbenzene insolubles and soluble fraction and the weight ethylene % that is present in each fraction.

Calculate the summation of weight ethylene % obtains total weight ethylene % (in polymkeric substance) according to equation 1 by each fraction.This mass balance equation also may be used for quantification binary blend or extends to the amount of each component in ternary or n unit blend of components.

Application equation 2 to 4, calculates the amount of the soft segment (providing the source of extra ethene) existed in insoluble fraction.By the C of insoluble fraction in alternative equation 2 left-hand side ₂% by weight, % by weight iPP is hard to be calculated with the soft equation 3 and 4 that can use of % by weight EP.Weight ethylene % during attention EP is soft is set as the weight ethylene % equaled in xylene-soluble fraction.If the weight ethylene % in iPP block is set as 0 or otherwise form method of masurement by its DSC fusing point or other and become known quantity, this value can be put into its position.

W _{eP is soft}=1-w _{iPP is hard}equation 4

After ' other ' ethene existed in insoluble fraction is described, make EP multipolymer be present in the unique method of insoluble fraction, EP polymer chain must be connected to iPP polymer blocks (otherwise it will extract into xylene-soluble fraction).Therefore, when the crystallization of iPP block, it prevents EP block from dissolving.

For evaluating block matrix material index, the relative quantity of each block must be considered.For close to this, use the soft iPP of EP hard between ratio.The ratio of EP flexible polymer and iPP hard polymer can use equation 2 by the mass balance calculation$ of the whole ethene recorded in polymkeric substance.Alternatively, its mass balance that also can be consumed by monomer in polymerization process and comonomer is estimated.For all tests, with reference to the assessment ratio of iPP and EP existed in Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock in table 3.The weight fraction that iPP is hard and the soft weight fraction of EP use equation 2 calculate and suppose that iPP does not comprise ethene firmly.The weight ethylene % that EP is soft is the amount of the ethene existed in xylene-soluble fraction.

Such as, if block matrix material of the present invention (C) comprises iPP (C) (i), EP (C) (ii) and iPP-EP diblock (C) (iii), comprises the C of 47wt% altogether ₂and in preparation, there is 67wt%C ₂eP flexible polymer and do not comprise ethene iPP homopolymer condition under prepare, the amount that the soft iPP of EP is hard is respectively 70wt% and 30wt% (use equation 3 and 4 calculate).If the per-cent of EP is 70wt% and iPP is 30wt%, so the relative ratios of EP:iPP block can be expressed as 2.33:1.

Therefore, if those skilled in the art carry out the xylene extraction of polymkeric substance and reclaim the insolubles of 40wt% and the solvend of 60wt%, this will be unforeseeable result and this can obtain conclusion, namely there is the fraction of segmented copolymer of the present invention.If the ethylene content measuring insoluble fraction is afterwards the C of 25wt% ₂, equation 2 to 4 can be solved this other ethene to be described and to obtain the EP flexible polymer of 37.3wt% and the iPP hard polymer of 62.7wt%.

Because insoluble fraction comprises the EP multipolymer of 37.3wt%, it should attach to the iPP polymkeric substance of other 16wt%, is 2.33:1 based on EP:iPP block ratio.This makes the evaluation quantity of diblock in insoluble fraction be 53.3wt%.For whole polymkeric substance (unassorted), composition is described as the iPP-EP diblock of 21.3wt%, the iPP polymkeric substance of 18.7wt%, and the EP polymkeric substance of 60wt%.Because the composition of these polymkeric substance is novel, term " block matrix material index " (or " BCI ") be defined as in the application equal diblock weight percent divided by 100% (i.e. weight fraction).The value of block matrix material index can be 0 to 1, and wherein 1 equals 100% diblock of the present invention, and 0 is material such as traditional blends or random copolymers.For example described above, the block matrix material index of block matrix material is 0.213.For insoluble fraction, BCI is 0.533, and for soluble fraction, the assignment of BCI is 0.

According to the estimation to total polymer composition with for estimating the error firmly and in the analysis to measure of the composition of soft segment, 5 to 10% errors are possible in the calculated value of block matrix material index.Such estimation comprises the wt%C2 in iPP hard block, is analyzed or processing condition measurement by DSC fusing point, NMR; By the average wt%C2 formed in the soft segment of estimation of xylene soluble part, or by NMR, or pass through the DSC fusing point (if detecting) of soft segment.But generally, block matrix material Index for Calculation suitably illustrates in insoluble fraction ' other ' ethene of the unforeseeable amount existed, make EP multipolymer be present in unique method in insoluble fraction, EP polymer chain must be connected to iPP copolymer block (otherwise it will extract into xylene soluble part fraction).

The method preparation by comprising the following steps of the block composite polymer of the application: make can the monomer of addition polymerization or the mixture of monomer under addition polymerization conditions with comprise at least one addition polymerization catalysts, promotor contacts with the composition of chain shuttling agent, the feature of described method is in two or more reactors operated under stable state polymerizing condition under diverse ways condition, or in two or more regions of the reactor operated under plug flow polymerization condition, form the polymer chain that at least some increases.

In one embodiment, block matrix material comprises the fraction of the block polymer of the distribution with most probable block length.It is the segmented copolymer comprising 2 or 3 blocks or segment according to the preferred polymkeric substance of the application.In the polymkeric substance comprising three or more segments (namely by distinguishing the block that block is separated), each block can identical or chemical difference, and the common distribution being characterised in that character.In the method preparing polymkeric substance, chain shuttles back and forth and is used as the method in the life-span extending polymer chain, make the signal portion of polymer chain with at least the first reactor leaving multiple reactors of series connection with the polymer form of chain shuttling agent end-blocking or the first reactor area of multizone reactor substantially operated under plug flow conditions, polymer chain experiences different polymerizing conditions in next reactor or the zone of convergency.Different polymerizing conditions in each reactor or region comprise the different monomer of use, comonomer, or monomers/comonomers ratio, different polymerization temperature, the pressure of various monomer or dividing potential drop, different catalysts, different monomer gradients, or cause forming other difference any can distinguishing polymer segment.Therefore, at least partially polymkeric substance comprise two kinds, three kinds, or more plant, be preferably the polymer segment of arrangement in two or three different molecule.

Based on theoretical derived parameter in the following mathematical processing theory of resulting polymers, think and prove, the flow reactor particularly connected at two or more steady state series or region (the different polymerizing conditions that the polymkeric substance with growth is exposed to), the block length of the polymkeric substance formed in each reactor or region will meet the most probable distribution of deriving in the following manner, and wherein pi is in the reactor about the probability that the polymer chain of the block sequence from catalyzer i increases.Theoretical treatment is based on standard hypothesis known in the art and method and for predicting the impact of polymerization kinetics for molecular structure, comprise use not by the mass action reaction rate laws that chain or block length affect, and following hypothesis: polymer chain increases and completes within the time extremely short compared with the average reactor residence time.W.H.Ray is had been disclosed in before such method, J.Macromol.Sci., Rev.Macromol.Chem., C8,1 (1972) and A.E.Hamielec and J.F.MacGregor, " Polymer Reaction Engineering ", K.H.Reichertand W.Geisler, Eds., Hanser, Munich, 1983.And, suppose given reactor medium chain shuttle back and forth reaction occur at every turn cause forming single polymer blocks, and the polymkeric substance of chain shuttling agent end-blocking is passed to different reactor or region and be exposed to different polymerizing condition and cause forming different blocks.For catalyzer i, the Sequence of length n obtained is in the reactor provided by Xi [n], and wherein n is positive number 1 to infinity, represents the sum of monomeric unit in block.

The most probable distribution of Xi [n]=(1-pi) pi (n-1) block length

the equal block length of number

If be present in reactor or region more than a kind of catalyzer, the chainpropagation of so each catalyzer has probability (pi) and therefore has average block length and the distribution of the uniqueness of the polymkeric substance prepared at this reactor or region.In most preferred embodiments, the definition of probability of chainpropagation is:

pi = \frac{Rp [i]}{Rp [i] + Rt [i] + Rs [i] + [Ci]}

For each catalyzer i={1,2...},

Wherein,

Rp [i]=consume the local velocity of monomer by catalyzer i, (mole number/L/ time),

The chain transmission of Rt [i]=catalyzer i and total speed of termination, (mole number/L/ time), and

The local velocity that the chain of Rs [i]=use dormancy polymkeric substance shuttles back and forth, (mole number/L/ time).

For given reactor, polymer chain rate of rise Rp [i] is as given a definition: observed rate constant be multiplied by total monomer concentration [M] and be multiplied by the local velocity [Ci] of catalyzer i, as follows:

Rp [i] = \overset{&OverBar;}{kpi} [M] [Ci]

Chain transmission, termination and speed of shuttling back and forth are defined as chain and are passed to hydrogen (H ₂), β hydrogen is eliminated, and chain is passed to the function of chain shuttling agent (CSA).Amount [H ₂] and [CSA] be volumetric molar concentration, each subscript k value is the rate constant in reactor or region:

Rt[i]=kH2i[H2][Ci]+kβi[Ci]+kai[CSA][Ci]

When polymer moieties is passed to CSA and whole CSA parts of assumed response are respective and dormancy polymer chain is paired, produce dormancy polymer chain.Provide as follows by the chain that catalyzer i obtains dormancy polymkeric substance speed of shuttling back and forth, wherein [CSAf] is the input concentration of CSA, and amount ([CSAf]-[CSA]) represents the concentration of dormancy polymer chain:

Rs[i]=kai[Ci]([CSAf]-[CSA])

Due to above-mentioned theory process, can see the total block length distribution of each block of gained segmented copolymer be before the block length distribution that provided by Xi [n] by the summation of the partial polymerization thing throughput rate weighting of catalyzer i.This represents that the polymkeric substance prepared under at least two kinds of different polymer formation conditions will have at least two kinds of diacritic blocks or segment, and each block or segment have most probable block length and distribute.

Suitable catalyzer and the catalyst precursor of preparing block matrix material (C) comprise metal complex, such as be disclosed in WO2005/090426, especially, the 53rd page of the 20th start of line those disclosed is walked to, by reference to being incorporated to the application at the 20th page the 30th.Suitable catalyzer is also disclosed in US2006/0199930; US2007/0167578; US2008/0311812; US7,355,089B2; Or WO2009/012215, wherein about the part of catalyzer by reference to being incorporated to the application.Suitable promotor is disclosed in those of WO2005/090426, is particularly disclosed in the 54th page the 1st and walks to those of the 60th page of the 12nd row, by reference to being incorporated to the application.Suitable chain shuttling agent is disclosed in those of WO2005/090426, is particularly disclosed in the 19th page the 21st and walks to those of the 20th page of the 12nd row, by reference to being incorporated to the application.Particularly preferred chain shuttling agent is dialkyl zinc compounds.

The block polymer of block matrix material comprises the propylene of polymerized form and ethene and/or one or more C _4-20alpha-olefin comonomer, and/or one or more in addition can the comonomer of copolymerization or they comprise 4-methyl-1-pentene and ethene and/or one or more C _4-20alpha-olefin comonomer, or they comprise 1-butylene and ethene, propylene and/or one or more C ₅-C ₂₀alpha-olefin comonomer and/or one or more in addition can the comonomer of copolymerization.Comonomer suitable is in addition selected from diolefine, cyclic olefin, and cyclic diene hydrocarbon, the vinyl compound of halogenation, and vinylidene aromatic compound.

Co-monomer content in gained block composition polymer can use any suitable commercial measurement, is preferably based on the technology of nucleus magnetic resonance (NMR) spectral method.Some or all polymer blocks of high expectations comprises amorphous or relatively unbodied polymkeric substance, such as following multipolymer: propylene, 1-butylene or 4-methyl-1-pentene and comonomer, particularly following random copolymers: propylene, 1-butylene or 4-methyl-1-pentene and ethene, and any remaining polymer blocks (hard segment), if exist any, mainly comprise the propylene of polymerized form, 1-butylene or 4-methyl-1-pentene.Preferably, such segment is highly crystalline or three-dimensional single-minded polypropylene, polybutene or poly-4-methyl-1-pentene, particularly isotaxy homopolymer.

Further preferably, the segmented copolymer of the application comprises 10 to 90% crystallizations or relative hard segment is amorphous with 90 to 10% or relative amorphous segment (soft chain segment), be preferably 20 to 80% crystallizations or relative hard segment or relative amorphous segment (soft chain segment) amorphous with 80 to 20%, most preferably be 30 to 70% crystallizations or hard segment or relative amorphous segment (soft chain segment) amorphous with 70 to 30% relatively.In soft chain segment, molar percentage comonomer can be 10 to 90 % by mole, is preferably 20 to 80 % by mole, most preferably is 33 to 75 % by mole.When comonomer is ethene wherein, its amount is preferably 10 % by mole to 90 % by mole, is more preferably 20 % by mole to 80 % by mole, most preferably is 33 % by mole to 75 % by mole.Preferably, multipolymer is included as 90 % by mole of hard segments to 100 % by mole of propylene.Hard segment for being greater than 90 % by mole, being preferably greater than 93 % by mole, being more preferably the propylene being greater than 95 % by mole, can most preferably be the propylene being greater than 98 % by mole.Such hard segment has corresponding fusing point, and it is 80 ° of C and higher, is preferably 100 ° of C and higher, is more preferably 115 ° of C and higher, most preferably is 120 ° of C and higher.Preferably, the segmented copolymer of the application comprises 10 to 90% crystallizations or relative hard segment or relative amorphous segment (soft chain segment) amorphous with 90 to 10%.In soft chain segment, molar percentage comonomer can be 5 to 90 % by mole, is preferably 10 to 60 % by mole.When comonomer is ethene wherein, its amount is preferably 10wt% to 75wt%, is more preferably 30wt% to 70wt%.

Preferably, multipolymer is included as the hard segment of 80wt% to 100wt% propylene.Hard segment can for being greater than 90wt%, being preferably greater than 95wt%, being more preferably the propylene being greater than 98wt%.

The block composition polymer of the application can distinguish over conventional random copolymer, the physical blending thing of polymkeric substance, and through adding segmented copolymer prepared by monomer continuously.Block matrix material may be different from random copolymers by following characteristics, the comparatively high melting temperature of such as a great deal of comonomer, blockiness index and block matrix material index, as described below; Physical blending thing is different from, such as blockiness index, block matrix material index, good tensile strength, the breaking tenacity of improvement, good form, the optical property of improvement by following characteristics, and in the larger shock strength of lesser temps; Be different from the segmented copolymer prepared by adding monomer continuously in the following areas: molecular weight distribution, rheology, shear shinning, rheology ratio, and different in the following areas: there is block polymolecularity.

In some embodiments, the block matrix material index (BCI) as hereafter defined of the block matrix material of the application is greater than 0 but is less than about 0.4 or for about 0.1 to about 0.3.In other embodiments, BCI is for being greater than about 0.4 and at the most about 1.0.In addition, BCI can be about 0.4 to about 0.7, about 0.5 to about 0.7, or about 0.6 to about 0.9.In some embodiments, BCI is about 0.3 to about 0.9, about 0.3 to about 0.8, or about 0.3 to about 0.7, about 0.3 to about 0.6, about 0.3 to about 0.5, or about 0.3 to about 0.4.In other embodiments, BCI is about 0.4 to about 1.0, about 0.5 to about 1.0, or about 0.6 to about 1.0, about 0.7 to about 1.0, about 0.8 to about 1.0, or about 0.9 to about 1.0.

Propylene, 1-butylene or 4-methyl-1-pentene and ethene according to the composition of the application needed for other, and the elastomeric block copolymers of one or more optional alpha-olefins or diene monomers.For the preferred alpha-olefin formula CH of this embodiment of the application ₂=CHR* represents, wherein R* is the alkyl with the linear of 1 to 12 carbon atom or branching.The example of the alpha-olefin be applicable to includes but not limited to iso-butylene, 1-butylene, 1-amylene, 1-hexene, 4-methyl-1-pentene (when with copolymerization of propylene), and 1-octene.Suitable diene for the preparation of these polymkeric substance (particularly many blocks EPDM type polymkeric substance) comprises the conjugation or unconjugated containing 4 to 20 carbon atoms, straight or branched, ring-type or polycyclic diene.Preferred diene comprises Isosorbide-5-Nitrae-pentadiene, Isosorbide-5-Nitrae-hexadiene, 5-ethylidene-2-norbornylene, Dicyclopentadiene (DCPD), cyclohexadiene and 5-fourth fork-2-norbornylene.Particularly preferred diene is 5-ethylidene-2-norbornylene.The isotaxy homopolymer segment replaced with elastomer copolymer segment that products therefrom can be included in prepared by polymerization process situ.Preferably, product only can comprise the elastomeric block copolymers of propylene, 1-butylene or 4-methyl-1-pentene and one or more comonomers (particularly ethene).

Because comprise the segment containing relatively large or diene comparatively in a small amount (comprise containing) and alpha-olefin (comprise containing) alternately or block containing the polymkeric substance of diene, so can when not losing polymer property subsequently by the total amount reduction of diene and alpha-olefin.That is, because diene and 'alpha '-olefin monomers are preferentially combined in the polymer blocks of a type, and non-homogeneous or randomly throughout whole polymkeric substance, therefore, they can efficiently be utilized, and the cross-linking density of polymkeric substance can be controlled better thereafter.This crosslinkable elastomeric and cured product have favourable character, comprise higher tensile strength and good elastic recovery.

In one embodiment, the weight-average molecular weight (Mw) of block matrix material is 10,000 to about 2,500,000, is preferably 35000 to about 1,000,000, is more preferably 50,000 to about 300,000, be preferably 50,000 to about 200,000.Block matrix material (C) is disclosed in the co-pending U.S. Patent application 61/248,160 submitted on October 2nd, 2009, and its full content is by reference to being incorporated to the application.

(ii) crystalline blocks matrix material

Block matrix material (C) can be crystalline blocks matrix material.Term " crystalline blocks matrix material " (CBC) refers to new polymers, it comprises the polymkeric substance (CEP) of crystallization based on ethene, crystallization is based on the polymkeric substance (CAOP) of alpha-olefin, with the segmented copolymer with crystalline ethylene block (CEB) and crystalline alpha-olefin block (CAOB), wherein the CEB of segmented copolymer is substantially identical with the composition of the CEP in block matrix material, and the CAOB of segmented copolymer is substantially identical with the composition of the CAOP in block matrix material.Segmented copolymer can be linear or branching.More particularly, each block segments can comprise the long chain branches that composition is similar to each block separately, but block copolymer segments substantial linear, contrary with the block comprising grafting or branching.When preparing with continuous processing, the PDI of crystalline blocks matrix material is desirably 1.7 to 15, is preferably 1.8 to 5, is more preferably 1.8 to 3.5, most preferably is 1.8 to 2.5.

CAOB refers to the highly crystalline block of the alhpa olefin unit of polymerization, and wherein the amount of monomer is for being greater than 90 % by mole, is preferably greater than 93 % by mole, is more preferably and is greater than 95 % by mole, be preferably greater than 96 % by mole.In other words, the co-monomer content in CAOB is less than 10 % by mole, is preferably less than 7 % by mole, is more preferably and is less than 5 % by mole, most preferably is and is less than 4 % by mole.Such CAOB has corresponding fusing point, and it is 80 ° of C and higher, is preferably 100 ° of C and higher, is more preferably 115 ° of C and higher, most preferably is 120 ° of C and higher.In some embodiments, CAOB comprises all or whole propylene units substantially.On the other hand, CEB represents the block of the ethylene unit of polymerization, and wherein co-monomer content is 10 % by mole or less, is preferably 0 % by mole to 10 % by mole, is more preferably 0 % by mole to 7 % by mole, most preferably is 0 % by mole to 5 % by mole.Such CEB has corresponding fusing point, and this fusing point is preferably 75 ° of C and higher, is more preferably 90 ° of C, and 100 ° of C and higher.

Preferably, the crystalline blocks composition polymer of the application comprises the CEP of 0.5 to 94wt%, the CAOP of 0.5 to 94wt% and the segmented copolymer of 5 to 99wt%.More preferably, crystalline blocks composition polymer comprises the segmented copolymer of the CEP of 0.5 to 79wt%, the CAOP of 0.5 to 79wt% and 20 to 99wt%, is more preferably the segmented copolymer of the CEP of 0.5 to 49wt%, the CAOP of 0.5 to 49wt% and 50 to 99wt%.

Preferably, the segmented copolymer of the application comprises the crystalline ethylene block (CEB) of 5 to 95wt% and the crystalline alpha-olefin block (CAOB) of 95 to 5%.They can comprise the CEB of 10wt% to 90wt% and the CAOB of 90wt% to 10wt%.More preferably, segmented copolymer comprises the CEB of 25 to 75wt% and the CAOB of 75 to 25wt%, and even more preferably, they comprise the CEB of 30 to the 70% and CAOB of 70 to 30wt%.

In some embodiments, the block matrix material of the application has crystalline blocks matrix material index (CBCI), and as given a definition, it is greater than 0 but is less than about 0.4 or for about 0.1 to about 0.3.In other embodiments, CBCI is greater than about 0.4 and at the most about 1.0.In addition, CBCI can be about 0.4 to about 0.7, about 0.5 to about 0.7, or about 0.6 to about 0.9.In some embodiments, CBCI is about 0.3 to about 0.9, about 0.3 to about 0.8, or about 0.3 to about 0.7, about 0.3 to about 0.6, about 0.3 to about 0.5, or about 0.3 to about 0.4.In other embodiments, CBCI is about 0.4 to about 1.0, about 0.5 to about 1.0, or about 0.6 to about 1.0, about 0.7 to about 1.0, about 0.8 to about 1.0, or about 0.9 to about 1.0.

Further preferably, the weight-average molecular weight (Mw) of the crystalline blocks matrix material of the application's embodiment is 1,000 to about 2,500,000, be preferably 35000 to about 1,000,000, be more preferably 50,000 to 500,000, be more preferably 50,000, to about 300,000, is more preferably 50,000 to about 200,000.Crystalline blocks matrix material and crystalline blocks matrix material index (CBCI) calculate the co-pending U.S. Patent application 61/356,978 being disclosed in and submitting on June 21st, 2010, and its full content is by reference to being incorporated to the application.

In one embodiment, block matrix material (C) comprises isotatic crystalline propylene homopolymer, or iPP (C) (i), ethylene/propene copolymer, or EP (C) (ii), and segmented copolymer (C) (iii).Segmented copolymer subgroup divides (C) (iii) to comprise the diblock with following formula (1).

(EP)-(iPP) (1)

Term " EP " represents the ethene of polymerization and the segment of propylene monomer units.Term " iPP " represents the segment of isotactic propylene homopolymer or the segment of basic isotactic propylene homopolymer, and they have minimum (<1%) atactic or syndiotaxy defect.

In one embodiment, the ethylene content of block matrix material (C) is greater than 20wt%, or is greater than 30wt%, or is greater than 35wt%.Weight ethylene per-cent is based on the gross weight of block matrix material (C).

In one embodiment, the amount of component (C) (iii) is greater than 15wt%, or is greater than 20wt%, or is greater than 25wt%, or is greater than 30wt%, or is greater than 50wt% to about 80wt%, based on the gross weight of component (C).

In one embodiment, the density of block matrix material (component C) is 0.865 to 0.90g/cc, or 0.897g/cc and/or melt index (I ₂) be 1 to 50g/10min.

In one embodiment, the melt index of block matrix material (C) is about 1, or about 2, or about 3, or about 4, or about 5, or about 6 to about 40, or about 35, or about 20, or about 15, or about 13.

In one embodiment, the I of block matrix material (C) ₁₀/ I ₂for about 6, or about 7, or about 8 to about 20, or about 19, or about 17, or about 15, or about 13, or about 12, or about 11.

D. based on the polymkeric substance of alkene

Inventive polymers composition optionally can comprise the polymkeric substance based on alkene.The limiting examples of the suitable polymkeric substance based on alkene comprises the polymkeric substance based on propylene and the polymkeric substance based on ethene.The limiting examples of the suitable polymkeric substance based on ethene comprises linear low density polyethylene (LLDPE), Low Density Polyethylene (LDPE), HDPE, the polyethylene of even branching (limiting examples comprises the polymkeric substance sold by ExxonMobil with trade name EXXACT and the polymkeric substance sold by Mitsui with trade name TAFMER), substantially linear ethene polymers (limiting examples comprises the polymkeric substance sold by The Dow Chemical Company with trade name AFFINTY and ENGAGE), the functionalized polymkeric substance based on alkene, and any combination.

In one embodiment, the polymkeric substance based on alkene can comprise the functionalized polymkeric substance based on alkene.The limiting examples of the suitable functionalized polymkeric substance based on alkene comprises the polyethylene of maleic anhydride graft, the polypropylene of maleic anhydride graft, ethylene acrylic acid co polymer, ethylene methyl acrylate copolymer, and any combination.

E. additive

Inventive polymers composition can optionally comprise one or more additives.Additives known can be incorporated in resin combination, as long as the object of the application is without prejudice.The limiting examples of such additive comprises nucleator, antioxidant, acid scavenger, thermo-stabilizer, photostabilizer, ultraviolet absorbers, lubricant, static inhibitor, pigment, dyestuff, dispersion agent, inhibitor, neutralizing agent, whipping agent, softening agent, flow improver, antiblocking agent, increases sliding additive, and welding strength activator.

Above-mentioned additive can combinationally use by any, and separately can the content in respective polymer composition be 0.0001 to 10% (or any independent value wherein or subrange) or be 0.001 to 1.0%.

Polymer composition can comprise two or more embodiments disclosed in the present application.

2. film

The application provides film, and it comprises Inventive polymers composition.In other words, Inventive polymers composition can be formed as film.In one embodiment, provide film, it comprises:

(A) polymkeric substance based on propylene of 1wt% to 50wt%;

(B) ethylene/alpha-olefin polymer of at least 50wt%, based on the gross weight of (A) and (B); With

(C) the block matrix material of 1wt% to 30wt%.

Film optionally can comprise polymkeric substance (D) based on alkene and/or additive (E).Component (A)-(E) can for above for any respective components (A)-(E) disclosed in polymer composition.In one embodiment, film comprises the component (A) of 5wt% to 50wt%, at least the component (B) of 50wt% to 95wt% and the component (C) of 1wt% to 30wt%.Weight percent is based on all wts of film.Film show one in the following following character stated for table 1, some or all.

Table 1-film character

Character	Unit	Scope
			Film thickness	Mill	0.3 to 5
Kinetic friction coefficient (F-F)		0.15 to 1.2
			Static friction coefficient (F-F)		0.15 to 1.2
Mist degree	%	0.5 to 15
			Transparency	%	80 to 99.5
Peak heat is adhered	N/in	3 to 18
			Hot sticky kick off temperature (HTIT)	°C	70-150
Peak heat stick temperature	°C	60 to 140
			Thermal bonding temperature window	°C	Wider than 50 ° of C, or wider than 55 ° of C,
At the Hot tack strength of 150 ° of C	N/in	1 to 8

Low-friction coefficient (COF) is the processing that strengthens and/or faster needed for package speed.Frictional coefficient in above table 1 is the frictional coefficient of film and film.The sealing stability that wide thermal bonding temperature window strengthens at sterilization temperature (120 ° of C to 130 ° of C) for (i) lower sealing kick off temperature (ii) and (iii) faster process velocity are favourable.The high Hot tack strength at 150 ° of C is favourable for germicidal applications.

Applicant has been found that the film with following required combination of properties: low COF, wide thermal bonding temperature window, low-heat adhesion kick off temperature, and at the high Hot tack strength of raised temperature.

And film of the present invention has the optical property of expectation: low haze and high-clarity.

In one embodiment, hot sticky the kick off temperature (HTIT) of film is less than 80 ° of C, or is less than 75 ° of C.

Film of the present invention can be unitary film.Inventive polymers composition can form the one or more layers in multilayer film.The structure of single/multiple film can be lamination, extrude (curtain coating/in flakes), coextrusion (curtain coating/in flakes), (single shaft, twin shaft, the tentering (tenter frame) of orientation, bubbling, double bubble, confines and bubbles (trapped bubble)), and combination.

In one embodiment, film of the present invention is without crosslinked.As used in this application, when the gel content of film is less than 5%, film is " without crosslinked ", measures according to ASTM D-2765-84 method A.

In one embodiment, the thickness of film is about 0.3 Mill to about 5.0 Mills, or about 3.5 Mills.

(A) multilayer film

The application provides multilayer film.In one embodiment, providing can multilayer film, and it comprises the first layer, the second layer and optional third layer.The first layer comprises:

(A) interpretation based on propylene of 1wt% to 50wt%,

(B) ethylene/alpha-olefin polymer of at least 50wt%, based on the gross weight of (A) and (B), and

(C) the block matrix material of 1wt% to 30wt%.

Weight percent is based on all wts of the first layer.Component (A), (B) and (C) can be any respective components (A)-(C) disclosed in Inventive polymers composition.The first layer can comprise optional component (D) and (E).

In one embodiment, the first layer component (B) is ethylene/alpha-olefin polymer, and its density is less than or equal to 0.91g/cc and/or melt index is 0.5g/10min to 25g/10min.

In one embodiment, the first layer component (C) of multilayer film comprises (i) iPP, (ii) ethylene/propene copolymer, and (iii) Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock, and it comprises iPP-block and ethylene/propene block.The density of block component (C) is 0.87g/cc, or 0.875g/cc to 0.915g/cc, or 0.92g/cc.

In one embodiment, the second layer of multilayer film comprises the polymkeric substance based on alkene.The limiting examples of the suitable polymkeric substance based on alkene comprises LLDPE, LDPE, the polyethylene of even branching, SLEP, HDPE, based on the polymkeric substance of propylene, and any combination.

In one embodiment, the second layer comprises the polymkeric substance based on alkene of 70wt% to 99wt% and the functionalized polymkeric substance based on alkene of 30wt% to 1wt%.The limiting examples of the suitable functionalized polymkeric substance based on alkene comprises the polyethylene of maleic anhydride graft, the polypropylene of maleic anhydride graft, ethylene acrylic acid co polymer, ethylene methyl acrylate copolymer, and any combination.The layer 2-based all wts of weight percent.

Optional third layer comprises and is selected from following material: nylon, polyethylene terephthalate (PET), polypropylene, and any combination.

In one embodiment, multilayer film is trilamellar membrane.The first layer is sealant layer (comprising Inventive polymers composition), and the second layer is sandwich layer (comprising the polymkeric substance based on alkene), and third layer is backing (comprises nylon, PET, and/or polypropylene).Sealant layer is innermost layer.The second layer is sandwich layer." sandwich layer " is the layer between at least two other layers.In other words, sandwich layer is not innermost layer or outermost layer.Backing is outermost layer.

In one embodiment, the thickness of trilamellar membrane is 0.3 Mill, or 0.5 Mill, Mill to 5, or 3 Mills.

Film of the present invention can comprise two or more embodiments disclosed in the present application.

3. goods

The application provides goods, and it comprises at least one assembly formed by Inventive polymers composition.In other words, Inventive polymers composition can be formed as goods.Inventive polymers composition and/or film of the present invention can be formed as finally manufacturing goods by any one in multiple ordinary method and equipment.Illustrative method includes but not limited to, extrudes, calendering, injection moulding, and/or compression moulding.Such as, goods can by injection moulding, extrude, extrude the preparations such as then thermoforming, low pressure molding, compression moulding.The limiting examples of suitable goods comprises the section bar (single or multiple lift film) extruded, foams, weather strip, band, flexible pipe, wire rod and cable chuck, pipe, flooring material, packing ring, molding kinds of goods, sheet material, and the parts extruded.Other goods comprise trolley part (such as, dashboard and window sealing member), machine element, material of construction, home appliances, toy, footwear component, label stock, carton box is milk box such as, pouch, bag, sack, sausage and/or pork pies fill or sealing bag, desiccating food products packaging such as grain, sugar, flour etc., the multilayer film of thermoforming, the container of thermoforming, blister packaging, and drug packages film.

(A) retort pouch

In one embodiment, goods are flexible container, and it comprises Inventive polymers composition.With reference to accompanying drawing, first with reference to Fig. 1, the goods showing a kind of form are retort pouchs, and it is represented by reference number 10 usually.As used in this application, " retort pouch " is soft package, and it can still keep airtight and sealing after the pressure 30-80 minute of the temperature and 500kPa at the most that are exposed to 120 ° of C-135 ° of C.Retort pouch 10 comprises two sheet material 12A and 12B of multilayer film, and they to be connected around their respective peripheries by heat seal thing 14 and are sealed.Heat seal thing 14 can extend along the whole common peripheral of sheet material 12A, 12B.Alternatively, heat seal thing 14 can extend along a part for the common peripheral of sheet material 12A, 12B.Storage area 16, by two sheet material 12A, limits in the region between 12B and heat seal thing 14.Storage area 16 and surrounding environment seal and separate and comprise the content 18 (such as food) of retort pouch.Although packaging is described as having two sheet material 12A, 12B, should be appreciated that and can use single sheet material.Single sheet material can fold and form two layers on themselves.So content can be placed on the post heat-seal stacked between layer by three edges do not connected.

The sheet material 12A of retort pouch 10,12B can by 2 film structure manufactures, as shown in Figure 2.Outer 20 from pack content 18 farthest.In one embodiment, the outer second layer corresponding to the film described before.

Sealant layer 22 is directly adjacent to outer 20.Sealant layer 22 (or innermost layer, or retort pouch content contact layer) comprise Inventive polymers composition.Skin 20 and sealant layer 22 can directly coextrusion each other.Alternatively, binder layer 24 can be combined outer 20 with sealant layer 22, as shown in Figure 2.Under the heat and pressure of relative sealant layer 24, the contact of film and film forms heat seal thing 14.

In one embodiment, before sterilization, retort pouch 10 is without wrinkle, or essentially no wrinkle.

In one embodiment, retort pouch 100 is made up of trilamellar membrane, as shown in Figure 3.Retort pouch 100 is similar to retort pouch 10, difference be retort pouch 100 by trilamellar membrane but not two membranes make.Sealant layer 22 contact layer 20.Backing 26 contact layer 20.Contact between layer can be " directly " (direct and/or close contact) or " indirectly " (intermediary adhesive layer between rete and/or intermediate structure).In this configuration, layer 20 (corresponding to the second layer of the film described before) becomes sandwich layer.Layer 26 is outermost layer and corresponds to the third layer of the film described before.

Layer 22,20, and the thickness of 26 can be identical or different.

In one embodiment, sealant layer 22 and sandwich layer 20 coextrusion.Backing 26 and sandwich layer 20 coextrusion.Sealant layer 22 and backing 26 are separately and layer 20 is direct and close contact.In other words, middle layer is not had to be present between sealant layer 22 and sandwich layer 20.Similarly, middle layer is not had to be present between backing 26 and sandwich layer 20.

In one embodiment, retort pouch 10 or retort pouch 100 comprise sealing coat.

Design retort pouch 10/100 reaches 30 to 90 minutes with the maximum applied temperature standing 120 to 135 ° of C (or any independent value wherein or subrange), and can not significantly degrade.

Retort pouch is used for splendid attire, protection or this nonrestrictive object of preservation, such as food, seasonings, medicine and sterilized solution.Retort pouch can be " pillow shape " or " reinforcing " or " uprightly " retort pouch.In " shaping and filling " packaging, retort pouch following (in line) is continuously formed: the bottom and the side seal place surface contact each other that make two films, add the material treating preservation, and form the final sealer enclosing food or other material to be packaged, whole operate continuously.Gained retort pouch is generally the bag of pillow shape.Alternatively, handler can use the pre-formed bags with single radial cut end, is then filled and closes after filling or sealing.This technology is applicable to reinforce retort pouch.In a final step, usually retort pouch and content are heated with pasteurization, sterilization or boiling content, such as, by using baking oven or being undertaken by steam under pressure in matrass.

Retort pouch can comprise two or more embodiments disclosed in the present application.

Definition

The all periodic table of elements mentioned of the application refer to be published by CRC Press, Inc. in 2003 and enjoys the periodic table of elements of copyright.Equally, any race mentioned should for using the race of reflecting in this periodic table of elements of the IUPAC system of numbering race.Unless pointed out, from context cues or prior art convention, all parts and per-cent are all based on weight.For the object of patent practice, any patent, patent application or disclosed content related to all is incorporated herein by reference (or the US of its equivalence is of the same clan be also incorporated herein by reference) at this, particularly about the disclosure of the synthetic technology in this area, definition (any definition specifically do not provided with the application is inconsistent) and general knowledge.

Any digital scope described in the application comprises all numerical value from lower value to higher limit increased with 1 unit, and condition is at any lower value and the interval that there are arbitrarily at least 2 units between high value.Such as, if the value of the amount of compositional, composition or physical properties, amount, softening temperature, melt index etc. as blend component are 1 to 100, mean that this specification sheets lists all single numerical value clearly, as 1,2,3 etc., and all subranges, as 1 to 20,55 to 70,197 to 100 etc.For the numerical value being less than 1, time suitable, regard 1 unit as 0.0001,0.001,0.01 or 0.1.These are only the examples of the content specifically meant, and likely combining of numerical value between cited Schwellenwert and maximum is all considered to know and records in this application.In other words, any digital scope described in the application comprises any value in described scope or subrange.As discussed in the present application, with reference to the digital scope that melt index, melt flow rate (MFR) and other character describe.

As used in this application, term " blend " or " blend polymer " are the blends of two or more polymkeric substance.Such blend can be or can not be miscible (not being separated at molecular level).Such blend can or can not be separated.Such blend can comprise or can not comprise one or more microcells structure, as determined by transmitted electron spectral method, scattering of light, x-ray scattering and any other method known in the art.

Term " composition ", as used in this application, the mixture comprising the material forming composition and the reaction product Sum decomposition product formed by each material of composition.

Term " comprises " and the existence of any annexing ingredient, step or process do not got rid of in derivative, and no matter whether the application disclosed them.For eliminating any query, unless illustrated, otherwise the composition that all use terms that this application claims " comprise " can comprise any additional additive, auxiliary material or compound (no matter whether being what be polymerized).On the contrary, except for unnecessary those of processing property, term " substantially by ... composition " get rid of other component any, step or process outside the how lower scope described in office.Term " by ... composition " do not comprise the component, step or the process that do not describe especially or list.Unless illustrated, otherwise term "or" refers to the separate member that lists or its any combination.

Term " polymkeric substance based on ethene " as used in this application, is comprise the vinyl monomer (weight based on polymkeric substance) and the polymkeric substance that optionally can comprise the comonomer that at least one is polymerized that are greater than 50 % by weight polymerizations.

" hot sticky kick off temperature " (HTIT) is hot sticky the temperature reaching 4N/ inch when seal temperature increases.

" thermal bonding temperature window " or " Δ T " is that wherein Hot tack strength is more than or equal to the temperature range of 5N/ inch.

Term " polymkeric substance based on alkene " is the polymkeric substance being greater than 50 % by weight alkene (such as ethene or propylene) comprising polymerized form, based on the weight of polymkeric substance.Limiting examples based on the polymkeric substance of alkene comprises the polymkeric substance based on ethene and the polymkeric substance based on propylene.

" polymkeric substance " is the macromolecular compound by making the monomer polymerization of identical or different type prepare." polymkeric substance " comprises homopolymer, multipolymer, terpolymer, interpretation etc.Term " interpretation " represents the polymkeric substance prepared by the monomer of at least two types or the polymerization of comonomer.It includes but not limited to multipolymer (it represents the polymkeric substance prepared by two kinds of dissimilar monomers or comonomer), terpolymer (it represents the polymkeric substance prepared by three kinds of dissimilar monomers or comonomer), tetrapolymer (it represents the polymkeric substance prepared by four kinds of dissimilar monomers or comonomer) etc.

Term " polymkeric substance based on propylene ", as used in this application, represents the propylene monomer (weight based on polymkeric substance) and the polymkeric substance that optionally can comprise the comonomer that at least one is polymerized that comprise and be greater than 50 % by weight polymerizations.

Testing method

Transparency is measured according to ASTM D1746.

The frictional coefficient of co-extruded films is measured between the film of outer (sealing agent) layer with outer (sealing agent) layer movement against blown film, measures in room temperature (23 ° of C) according to ASTM D1894.A slice film is fixed in horizontal beds.Be connected to below planker (sled) by another sheet film (for about 2.5 × 3 inches), this planker is placed on the top of planar film bed.TMI monitor/Slip & Friction Tester, model 32-06-00 is for measuring COF.Pulling speed is 6 inch per minute clocks.Record causes relative movement and keeps the power needed for steady motion and be respectively used to obtain static friction coefficient and kinetic friction coefficient.Value is the mean value of 5 readings.

Degree of crystallinity-dsc (DSC) is for measuring the degree of crystallinity of (PE) sample based on ethene and (PP) sample based on propylene.Sample is pressed into film in the temperature of about 190 ° of C.The membrane sample of about 5 to 8mg is weighed and puts into DSC dish.Make lid curling to guarantee the atmosphere closed on dish.Sample disc is placed in DSC groove, is then heated to for PE temperature 180 ° of C (being 230 ° of C for PP) with the speed of about 10 ° of C/min.Sample is made to keep 3 minutes in this temperature.Then sample is cooled to-60 ° of C (for-40 ° of C for PP) for PE with the speed of 10 ° of C/min, and constant temperature remains on this temperature 3 minutes.Then with the speed heated sample of 10 ° of C/min, until melting completely (the second heating).Percent crystallinity calculates as follows: by the Heat of fusion (H determined by the second heating curve _f) divided by the 292J/g (being 165J/g for PP) for PE theoretical Heat of fusion and be multiplied by 100 (such as, % degree of crystallinity=(H _f/ 292J/g) x100 (for PE)).

Density is measured according to ASTM D792-08.

Mist degree is measured according to ASTM D1003.

The heat-seal strength of film uses Enepay MAGMA hot sticky and measures with heat seal test macro.Film is sealed at assigned temperature, makes it be cooled to room temperature (23 ° of C) completely.Before test, by sample at 23 ° of C and minimum 24 hours of 50% regulation of relative humidity.The sample film with heat seal thing is prepared in following examples part.

Hot sticky test-sample film (preparing in following examples part) uses Enepay MAGMA hot sticky with heat seal test macro (purchased from Enepay Corporation, Raleigh, NC), based on ASTM F1921, method B according to following conditioned measurement:

Hot sticky the test condition of the film of table 2. coextrusion

Parameter	Unit	Value
			Specimen width:	mm	25.4
Sealing period:	Sec.	1.0
			Sealing load:	N/mm ²	0.275
Time of lag:	Sec.	0.1
			Pulling speed:	Mm/s	200

Hot sticky data are collected with 10 ° of C temperature increments.

Melt flow rate (MFR) (MFR) uses 2.16kg weight measurement according to ASTM D1238 testing method at 230 ° of C.

Melt index (MI) uses 2.16kg weight measurement according to ASTM D1238 testing method at 190 ° of C.

The melt temperature (Tm) of polymer samples is measured by dsc (DSC).Sample is pressed into film in the temperature of 190 ° of C.The membrane sample of about 5 to 8mg is weighed and puts into DSC dish.Make lid curling to guarantee the atmosphere closed on dish.Sample disc is placed in DSC groove, is then heated to for PE temperature 180 ° of C (being 230 ° of C for PP) with the speed of about 10 ° of C/min.Sample is made to keep 3 minutes in this temperature.Then sample is cooled to-60 ° of C (for-40 ° of C for PP) for PE with the speed of 10 ° of C/min, and constant temperature remains on this temperature 3 minutes.Then with the speed heated sample of 10 ° of C/min, until melting completely (the second heating).The fusing point of material is that material becomes liquid temperature from solid-state.Fusing point the application of polymkeric substance is defined as the temperature that Heat of fusion reaches maximum value.

Without restriction, embodiments of the invention will be provided by example.

Embodiment

1. polymer composition

Block matrix material, the co-pending U.S. Patent application 61/248 that component (C) was submitted to according on October 2nd, 2009, in 160 described preparation, its full content is by reference to being incorporated to the application.

The polymerizing condition producing block matrix material enforcement example 02,03 and 14 is provided in following table 3A-3D.The physical properties of gained block matrix material 02,03 and 14 is provided in table 4.

Catalyst system comprises catalyzer ([[rel-2', 2'''-[(1R, 2R)-1,2-hexanaphthene two base two (methylene radical oxygen base-κ O)] two [3-(9H-carbazole-9-base)-5-methyl [1,1'-biphenyl]-2-positive oxygen ion (olato)-κ O]] (2-)] dimethyl-hafnium) and promotor, methyl two (C _14-18alkyl) mixture of four (pentafluorophenyl group) boride of ammonium salt, it is substantially as USP5, disclosed by the embodiment 2 of 919,9883, by long-chain trialkylamine (Armeen ^tMm2HT, can derive from Akzo-Nobel, Inc.), HCl and Li [B (C ₆f ₅) ₄] reaction and prepare, can to use without the need to being further purified purchased from Boulder Scientific.

Catalyst system also comprises CSA (zinc ethyl or DEZ), and the methylaluminoxane (MMAO) of modification is purchased from Akzo Nobel and can use without the need to being further purified.The solvent of polyreaction is that hydrocarbon mixture (SBP100/140) can derive from Shell Chemical Company and before the use by the bed purifying of 13-X molecular sieve.

Example implemented by each block matrix material, and namely 02,03, and 14 comprise

(i) crystalline isotactic propylene homopolymer (iPP);

(ii) ethylene/propylene polymers (EP); With

(iii) segmented copolymer (diblock) of iPP-block and EP-block is comprised.

Table 4 provides block matrix material to implement the analysis and summary of example 02,03 and 14.Except as otherwise noted, the character in table 4 is the character of block matrix material (C).

Table 4. block matrix material, the analysis and summary-embodiment of component (C)

2. film

Before adding the hopper of forcing machine to, by component (A), (B) and (C) dry blend.To comprise (A) propylene/alpha-olefins interpretation, (B) is membrane structure based on the polymkeric substance of ethene and the polymer composition coextrusion of (C) block matrix material.

Three-layer co-extruded membrane uses the Colin extruded blown film production line manufacture with three forcing machines.Film manufacturing condition is shown in following table 5.Nylon Ultramid C33L01 is used as backing (there is bubble inside).90wt%ATTANE4201 (class of trade ultra-low density polyethylene/octene copolymer, purchased from DowChemical Company) and 10wt%AMPLIFY GR205 (the polymkeric substance HDPE of maleic anhydride graft, purchased from The Dow Chemical Company) blend be used as sandwich layer.Sealant layer composition and each trilamellar membrane character are shown in table 6.

The component of sealing ply is provided in following table 5A.

Table 5A. sealing ply component

Polymkeric substance	MI/MFR	Density
			(B)Affinity PL1880	1.0	0.902
(A)H110-02N	2.0*	0.902
			(A)DS6D81	5.0*	0.900
(C) block matrix material (14, derive from table 3,4)	5.8*	0.8997

At the MI that 190 ° of C2.16Kg record.

* at the MFR that 230 ° of C, 2.16kg record.

3 layers of extrusion condition of table 5B. coextrusion

The composition of table 6. sealant layer and the character of trilamellar membrane

Thermal bonding temperature window

Use concrete membrane structure, the co-extruded films prepared with Inventive polymers composition shows and is greater than the hot sticky of 5N/in in following temperature range, temperature range is at least about 40 ° of C, or at least about 45 ° of C, or at least about 50 ° of C (table 6), based on ASTM F1921, method B, wherein the residence time is 1.0 seconds and cooling time is 0.1 second.Thermal bonding temperature window data is shown in Fig. 6.

Hot sticky kick off temperature (HTIT)

Compared with comparative sample, the co-extruded films prepared of Inventive polymers composition shows suitable or lower hot sticky kick off temperature at sealant layer.Usually, lower hot sticky kick off temperature is expect for improving for the processing of packaging operation and throughput rate.With comprise the film of SLEP in sealant layer compared with, the co-extruded films comprising Inventive polymers composition in sealant layer has lower HTIT.HTIT data are listed in table 6 and are shown in Fig. 7.

Frictional coefficient (COF)

Usually, lower COF for strengthen processing and/or faster package speed be required.COF data presentation is in table 6 and Fig. 9.Compare with the comparative sample prepared based on polyacrylic polymkeric substance with SLEP, the co-extruded films with the sealant layer prepared with Inventive polymers composition shows lower COF.

At the Hot tack strength of raised temperature

Another very useful aspect of the embodiment of the present invention be they at raised temperature such as at the Hot tack strength of 150 ° of C.The higher Hot tack strength at high temperature allows at the temperature packaging raised and/or contents processing thing, such as, to heat machine-processed sterilizing, for germicidal applications through boiling water or other.As shown in Figure 10 and table 6, the embodiment of the present invention at the hot sticking value of 150 ° of C higher than this value of corresponding comparative sample.

Optical property

The optical property that embodiment of the present invention display is very good, as shown in table 6 and Figure 11.Comprise the transparence value of the film of the sealing agent of comparative sample and the embodiment of the present invention all higher than 90%.

Should pay special attention to, the application is not limited to embodiment that the application comprises and explanation, but comprising the modification of those embodiments following, described embodiment comprises the part of the embodiment within the scope of claims and the combination of different embodiment key element.

Claims

1. polymer composition, comprises:

(A) based on the polymkeric substance of propylene;

(B) at least the density of 50wt% is less than or equal to the ethylene/alpha-olefin copolymer of 0.91g/cc, based on the gross weight of (A) and (B); With

(C) block matrix material, it comprises:

I) based on the crystalline polymer of propylene;

Ii) ethylene/alpha-olefin polymer; With

2. the polymer composition of claim 1, the wherein said polymkeric substance based on propylene (A) is selected from alfon and propylene/ethylene copolymer.

3. the polymer composition of claim 1, wherein said ethylene/alpha-olefin copolymer (B) comprises the ethylene/alpha-olefin copolymer of even branching.

4. the polymer composition of claim 1, wherein said ethylene/alpha-olefin copolymer (B) comprises substantially linear ethene/alpha-olefin copolymer.

5. the polymer composition of claim 1, the melt index of wherein said ethylene/alpha-olefin copolymer (B) is 0.5g/10min to 25g/10min.

6. the polymer composition of claim 1, wherein said segmented copolymer (C) (iii) comprises the diblock with following formula (1):

(EP)-(iPP) (1)

Wherein EP represents the ethene of polymerization and the segment of propylene monomer units, and iPP represents the segment of isotactic propylene homopolymer.

7. the polymer composition of claim 1, wherein block matrix material (C) comprises (C) (iii) being greater than 15wt%, based on the total mass of block matrix material (C).

8. the polymer composition of claim 1, wherein the density of block matrix material (C) is 0.88g/cc to 0.90g/cc and melt index is 1g/10min to 50g/10min.

9. the polymer composition of claim 1, also comprise (D) polymkeric substance based on alkene, it is selected from linear low density polyethylene, Low Density Polyethylene, high density polyethylene(HDPE), the polyethylene of even branching, substantially linear ethene polymers, the functionalized polymkeric substance based on alkene, and combination.

10. film, it comprises at least one layer formed by the polymer composition of any one of claim 1-9.

11. films, comprising:

Comprise the first layer of the polymer composition of any one of claim 1-9; With

Comprise the second layer of the polymkeric substance based on alkene.

The film of 12. claims 11, the wherein said second layer comprises the polymkeric substance based on alkene and optionally comprises the functionalized polymkeric substance based on alkene.

13. retort pouchs, comprising:

Comprise the first layer of the polymer composition of any one of claim 1-9;

Comprise the second layer of the polymkeric substance based on alkene; With

Optional third layer.

The retort pouch of 14. claims 13, wherein said the first layer is sealant layer, and the described second layer comprises the polymkeric substance based on alkene based on the polymkeric substance of alkene and the functionalized of 30wt% to 1wt% of 70wt% to 99wt%.

The retort pouch of 15. any one of claim 13-14, wherein said third layer comprises and is selected from following material: nylon, polyethylene terephthalate (PET), polypropylene, and combination.